Effect of Ta2O5 Substituting on Thermal and Optical Properties of High Refractive Index La2O3–Nb2O5 Glass System Prepared by Aerodynamic Levitation Method

High refractive index glasses with nominal composition of 0.35La₂O₃–(0.65?x)Nb₂O₅–xTa₂O₅ (x ≤ 0.35) were prepared by aerodynamic levitation method. The effect of Ta₂O₅ substituting on their thermal and optical properties was investigated. All the glasses obtained were colorless and transparent. Differential thermal analyzer results show that as the content of Ta₂O₅ increased, the thermal stability of the glasses increased but the glass‐forming ability decreased. The transmittance spectra of all the obtained glasses exhibited a wide transmittance window ranging from 380 to 5500 nm. As the content of Ta₂O₅ increased, the refractive index of the glasses was enhanced from 2.15 to 2.21 and the dispersion was reduced with the Abbe number increasing from 20 to 27.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Novel gallate-based oxide and oxyfluoride glasses with wide transparency,high refractive indices,and low dispersions

The glass-forming region of a BaO-La₂O₃-Ga₂O₃ ternary system was confirmed and BaF₂-BaO-La₂O₃-Ga₂O₃ new oxyfluoride glasses were prepared by a containerless processing. We also analyzed the physical, thermal, and optical properties of new oxide and oxyfluoride glasses. The direct effects of the substitution of oxygen by fluorine and the effect of BaO and La₂O₃ on the refractive index and Abbe number were discussed on the basis of electronic polarizability and resonance wavelength of oscillator. The refractive indices increased with increasing La₂O₃ concentration because La₂O₃ increased the electronic polarizabilities. Abbe number increased with increasing BaO and fluorine concentration because of the decrease in resonance wavelength of oscillator. By the combination of the BaO, La₂O₃, and fluorine in the gallate glass system, we could obtain novel oxide and oxyfluoride glasses with high refractive index (1.81-1.95) and high Abbe number (31-55). The absorption edge in UV region shifted to the shorter wavelength and IR cut-off wavelength shifted to the longer wavelength with increasing fluorine. Therefore, wide transparent glass was obtained from 262 nm to 11.3 μm.     

Tunable ultra-wideband NIR emission and irradiation resistance in novel Er3+/Tm3+/Pr3+ tri-doped La2O3- Ga2O3-Ta2O5 glasses synthesized using aerodynamic levitation method

Glasses with ultra-wideband near-infrared emission and superior irradiation resistance are important for the potential applications in optical communications under harsh environments. Here, transparent 35La₂O₃-(65-x)Ga₂O₃-xTa₂O₅ (LGT) and Er³⁺/Tm³⁺/Pr³⁺ tri-doped LGT glasses are fabricated using the levitation method. LGT glasses exhibit a wide glass-formation region, low largest vibration energy, high refractive indices, and excellent mechanical properties. Additionally, Er³⁺/Tm³⁺/Pr³⁺ tri-doped LGT samples with varying Pr³⁺ contents are characterized by possessing good thermal stability (T_g>849°C), wide transparent optical window, strong radiation resistance, excellent compatibility between low wavelength dispersion (v_d>31.2), and large refractive index (n_d>2.048). By optimizing the doping content of Er³⁺, Tm³⁺, and Pr³⁺ in an appropriate ratio, the ultra-wideband near-infrared luminescence ranging from 1250 to 1640 nm (FWHM = 251 nm) has been acquired under 808 nm pumping. Furthermore, decay curves are measured to reveal the fluorescence dynamics, and then the related emission mechanism is elaborated systematically. Meanwhile, the effects of gamma irradiation doses on microstructure, transmittance spectra, and fluorescence characteristics are studied. This work may offer a valuable reference for doping optimization and new design strategy of multifunctional materials.     

High‐Temperature Phase Relations in the Lu2O3–Ta2O5 System

The compounds formed from the Lu₂O₃–Ta₂O₅ system in the composition range 25–60 mol% Ta₂O₅ were prepared by solid‐state reaction from 1350°C to 2058°C, and the phase transitions were investigated by X‐ray diffraction (XRD). Cubic Lu₃TaO₇, M′‐LuTaO₄, M‐LuTaO₄, O‐Ta₂O₅, and T‐Ta₂O₅ are observed. With the temperature increase, there is an irreversible phase transition from M′ to M‐LuTaO₄ near 1770°C in the composition of 30–52 mol% Ta₂O₅, and another phase transition from T‐Ta₂O₅ to O‐Ta₂O₅ at about 1685°C when the ratio of Ta₂O₅ is >52 and ≤60 mol%. A phase diagram of the Lu₂O₃–Ta₂O₅ system in the range 0–100 mol% Ta₂O₅ was constructed. These results are helpful to explain the phase transition of Lu₂O₃–Ta₂O₅ system and design the preparation technique of LuTaO₄ single crystal or ceramic scintillator, which may be applied in the fields of nuclear medicine and high‐energy physics.     

Frequency and Temperature‐Independent Electrical Transport Properties of 2BaO–0.5Na2O–2.5Nb2O5–4.5B2O3 Glass‐Ceramics

The temperature (300–973 K) and frequency (100 Hz–10 MHz) response of the dielectric and impedance characteristics of 2BaO‐0.5Na₂O–2.5Nb₂O₅–4.5B₂O₃ glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100 Hz–10 MHz) and temperature (300–600 K). The temperature coefficient of dielectric constant was 8 ± 3 ppm/K in the 300–600 K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal‐glass interface, leading to a high value of effective dielectric constant especially for the samples heat‐treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P_r) increased with the increase in crystallite size.     

Mid‐IR transparent TeO2‐TiO2‐La2O3 glass and its crystallization behavior for photonic applications

In this report, effect of enhanced rare earth (La₂O₃) concentration on substitution of TeO₂ within ternary TeO₂‐TiO₂‐La₂O₃ (TTL) glass system has been studied with respect to its thermal, structural, mechanical, optical, and crystallization properties with an aim to achieve glass and glass‐ceramics having rare‐earth‐rich crystalline phase for nonlinear optical and infrared photonic applications. DSC analysis (10°C/min) demonstrates a progressive increase in glass‐transition temperature (T_g) from 359 to 452°C with the increase in La₂O₃ content. Continuous glass network modification with transformation of [TeO₄] to [TeO₃/TeO₃₊₁] units is evidenced from Raman spectra which is corroborated with XPS studies. While mechanical properties demonstrate enhancement of cross‐linking density in the network. These glasses exhibit optical transmission window extended from 0.4 to 6 μm with calculated zero dispersion wavelength (λ_ZDW) varying from 2.41 to 2.28 μm depending upon La₂O₃ content. Crystallization kinetics of TTL10 (80TeO₂‐10TiO₂‐10La₂O₃ in mol%) glass has been studied via established models. Activation energy (E_a) has been evaluated and dimensionality of crystal growth (m) suggests formation of surface crystals. Glass‐ceramic with crystalline phase of La₂Te₆O₁₅ has been realized in heat‐treated TTL10 glass samples (at 450°C). As predicted from DSC analysis, FESEM study unveils the formation of surface crystallized glass‐ceramics.     

Radiation response properties of Eu3+-doped K2O–Ta2O5–Ga2O3 glasses

Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were synthesized, and their radiation response characteristics were studied systematically. According to their photoluminescence spectra, they showed intense emissions with sharp peaks centered at around 580, 594, 613, 656, and 706 nm when irradiated by 380 nm light. The sharp peaks originate from the 4f-4f transitions of Eu³⁺. Moreover, these sharp peaks were also detected when excited by X-ray, and the 1.0% Eu₂O₃-doped gallate glasses showed the largest luminescence intensity under UV light and X-ray. Furthermore, the afterglow levels of the Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were determined to be approximately 300 ppm. These levels are close to the levels of TI-doped CsI single crystals.     

Glass Formation and Characterization Studies in the TeO2–WO3–Na2O System

Glass formation behavior of the TeO₂–WO₃–Na₂O system was studied by using conventional melt‐quenching technique. A wide glass formation range was determined for the first time in the literature and thermal, physical, and structural characterization of sodium‐tungsten‐tellurite glasses were realized using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. Glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (?T), density (ρ), molar volume (V_M), oxygen molar volume (V_O), and oxygen packing density (OPD) values and structural transformations in the glass network were investigated according to the equimolar substitution of TeO₂ by Na₂O+WO₃ and changing Na₂O or WO₃ at constant TeO₂.     

New calcium‐free Na2O–Al2O3–P2O5 bioactive glasses with potential applications in bone tissue engineering

Sodium aluminophosphate glasses were evaluated for their bone repair ability. The glasses belonging to the system 45Na₂O–xAl₂O₃‐(55‐x)P₂O₅, with x = (3, 5, 7, 10 mol%) were prepared by a melt‐quenching method. We assessed the effect of Al₂O₃ content on the properties of Na₂O–Al₂O₃–P₂O₅ (NAP) glasses, which were characterized by density measurements, DSC analyses, solubility, bioactivity in simulated body fluid and cytocompatibility with MG‐63 cells. To the best of our knowledge, this is the first investigation of calcium‐free Na₂O–Al₂O₃–P₂O₅ system glasses as bioactive materials for bone tissue engineering.     

Synthesis and Characterization of Eu3+‐Doped Transparent Glass–ceramics Containing Nanocrystalline SrIINbIVO3

The glass–ceramics containing a rarely achievable nanocrystalline Sr^IINb^IVO₃ phase in the 53.75SiO₂–18.25K₂O–9Bi₂O₃–9SrO–9Nb₂O₅–0.5CeO₂–0.5Eu₂O₃ (mol%) glass system were prepared by the melt‐quench technique followed by a two‐stage controlled heat treatment. The unusual oxidation state of Nb in Sr^IINb^IVO₃ crystal is 4+ and upon heat treatment of the samples at lower temperature of 500°C for several hours, the glass composition and chemical environment around Nb ions played a key role for the formation of Sr^IINb^IVO₃ in the glass–ceramics. The microstructure of the glass–ceramics was studied using TEM and FESEM. The TEM images advocate 10–40 nm crystallite size of Sr^IINb^IVO₃. FTIR study confirms that all the samples consist of SiO₄, BiO₃, BiO₆, and NbO₆ structural units. The refractive index at different wavelengths was found to vary in the range 1.7105–1.7905 and increase with increase in heat‐treatment time. The luminescence spectra of Eu³⁺‐doped glass and glass–ceramics were recorded at 465 nm excitation wavelength and the luminescence intensity is found to be increased with heat‐treatment time due to increase in crystallinity. The high intensity ratio of ⁵D₀→⁷F₂ to ⁵D₀→⁷F₁ indicates that the Eu³⁺‐doped nanocrystalline Sr^IINb^IVO₃ glass–ceramics are promising candidate materials as red‐light source.     

A low sintering temperature glass based on SiO2–P2O5–ZnO–B2O3–R2O system for white LEDs with high color rendering index

A low sintering temperature glass based on the SiO₂–P₂O₅–ZnO–B₂O₃–R₂O (R=K and Na) system was studied as a matrix for embedding phosphors to fabricate color tunable white LEDs. The proposed system, which uses no heavy‐metal elements and can be sintered at 500°C, incorporates thermally weak commercial phosphors such as CaAlSiN₃:Eu²⁺ to produce phosphor‐in‐glasses (PiGs). Changing the mixing ratio of glass to phosphors affected the photo‐luminescence spectra and color coordinates of the PiGs when mounted on a blue LED. The color rendering index (CRI) and color correlated temperature (CCT) of the LEDs were also varied with the mixing ratio, providing color tunable white LEDs. A high CRI, up to 93, as well as highly improved thermal stability were obtained, along with a low sintering temperature compared to other glass systems, suggesting the practical feasibility of the proposed system.     

Preparation and characterizations of tantalum pentoxide (Ta2O5) nanoparticles and UV‐curable Ta2O5‐acrylic nanocomposites

Tantalum pentoxide (Ta₂O₅) nanoparticles with the sizes in the range of 20–50 nm were prepared via a chemical route in which the oleic acid (OLEA) was adopted as the surfactant for the synthesis process. X‐ray diffraction (XRD) revealed the as‐synthesized Ta₂O₅ transforms from amorphous to hexagonal and orthorhombic structures at the temperatures of 700°C and 750°C, respectively, illustrating the suppression of recrystallization temperature of Ta₂O₅ due to the particle size reduction. UV‐curable nanocomposites containing the Ta₂O₅ nanoparticles and acrylic matrix were also prepared. Thermogravimetry analysis (TGA) found an about 10–20°C improvement on the 5% weight‐loss thermal decomposition temperatures (T_ds). Dielectric measurement showed that the dielectric constant of nanocomposite increases with the increase in the filler loading without severe deterioration of dielectric loss. The increment of dielectric constants was ascribed to the addition of high‐dielectric inorganic fillers as well as the presence of interfacial polarization at the organic/inorganic interfaces. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Glass Formation and Ionic Conduction Behavior in GeSe2–Ga2Se3–NaI Chalcogenide System

Series of glassy and glass‐ceramic samples in the GeSe₂–Ga₂Se₃–NaI system is prepared by melt‐quenching technique and the glass‐forming region is well‐defined by XRD investigations. Na‐ion conduction behavior is systemically studied by impedance measurements. For the glasses in the series (100?2x)GeSe₂–xGa₂Se₃–xNaI, ionic conductivities increased with increasing x, whereas the attributed activation energy of ion conduction decreases. The enhanced mechanism is discussed by employing Raman spectra. In addition, the effect of the crystal phases NaI and Ga₂Se₃ on the ionic conduction behavior in the (70?x)GeSe₂–xGa₂Se₃–30NaI samples is discussed. Although it shows that the poorly conducting crystallites of NaI and Ga₂Se₃ have a negative effect on the ionic conductivities in this series, the highest ionic conductivity of 1.65 × 10^?6 S/cm is obtained in the 45GeSe₂–25Ga₂Se₃–30NaI glass. Finally, this study also demonstrates a possible way to search appropriate Na‐ion solid electrolytes for all‐solid‐state batteries.     

High‐Performance Ferroelectric Solid Solution Crystals: Pb(In1/2Nb1/2)O3–Pb(Zn1/3Nb2/3)O3–PbTiO3

A series of regular shaped Pb(Zn_1/3Nb_2/3)O₃‐based ternary ferroelectric single crystals (1 ? x)Pb(In_1/2Nb_1/2)O₃–0.33Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PIN–PZN–PT) have been grown by means of the top‐seeded solution growth method that prevented pyrochlore phase and promoted [001] or [111] growth. The nucleation and crystallization behavior of the Pb(Zn_1/3Nb_2/3)O₃‐based ferroelectric single crystals differed from other relaxor‐based ferroelectric single crystals was discovered. Di‐/piezo‐/ferro‐/pyroelectric properties were characterized systematically. The PIN–PZN–PT single crystals showed large coercive fields E_c, high Curie temperature T_C and high pyroelectric coefficient P, presenting similar performance but better thermal stability compared with the PZN–PT single crystals, and making it a promising material for transducers and IR detectors in a wider temperature range.     

Compositional dependence of the optical properties of novel Ga–Sb–S–XI (XI = PbI2, CsI,AgI) infrared chalcogenide glasses

A novel family of Ga₂S₃–Sb₂S₃–XI (XI = PbI₂, CsI, AgI) was investigated to understand the role of metal halides and exploit new chalco‐halide glasses for infrared optics. The dependence of the thermal properties, infrared optical properties, and structural information of the novel family on different metal–iodines was investigated. Results showed that metal halides increase the glass stability but decrease the glass network connectivity. The compositional dependence of the short‐wave cut‐off edge is associated with the electronegativity difference between the cations and anions of the metal halides. Raman study showed that the metal–iodine modified the glass structure mainly through the iodide content, and the cations dissolved in the glass network mostly as charge compensators for the aperiodic network. For the glasses in the series Ga₂S₃–Sb₂S₃–XI–Dy³⁺, Dy³⁺ emission increased in the PbI₂‐ and CsI‐doped glasses but decreased in the AgI‐doped glass due to the combined effect of dysprosium and oxygen. For all that, these novel glasses are highly promised for use in infrared optics.     

Surface Analysis of Cr2O3‐, CoO‐, and Al2O3‐Doped Iron–Phosphate Glasses at High Temperature

Surface structures of iron–phosphate glasses were examined using X‐ray photoelectron spectroscopy (XPS). Cr₂O₃, CoO, and Al₂O₃ were introduced to the glass by the replacement of a part of Fe₂O₃, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC‐1 test. In situ high‐temperature and room‐temperature XPS measurements were conducted on the polished sample surfaces and also those after 1‐week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition‐metal ions.     

Coloration and Nonlinear Optical Properties of ZnTe Quantum Dots in ZnO–TeO2–P2O5 Glasses

ZnO–TeO₂–P₂O₅ glasses were prepared by melt‐quenching method. The color of the glass samples changed from colorless to pale red and dark red with increasing TeO₂ content. Coloration mechanism and nonlinear optical properties of ZnO–TeO₂–P₂O₅ glasses have been investigated. Raman spectra and transmission electron microscope measurements indicated the precipitation of ZnTe quantum dots in the glasses and ZnTe quantum dots are the origin of coloration. Z‐scan technique was used to examine the nonlinear optical properties of the glasses. The glass sample with 30 mol% TeO₂ exhibits large third‐order nonlinear optical susceptibility of 10^?11 esu.